Polyol formed from an EPOXIDIZED oil

ABSTRACT

A polyol includes the reaction product of an epoxidized oil and an organic acid. The epoxidized oil and the organic acid are reacted in the presence of a Lewis base catalyst including at least one of a phosphorous atom or a nitrogen atom. The polyol is formed by a method that includes the step of reacting the epoxidized oil with the organic acid in the presence of the Lewis base catalyst.

FIELD OF THE INVENTION

The present invention generally relates to a polyol and a method offorming the polyol. More specifically, the polyol is the reactionproduct of an epoxidized oil and an organic acid which are reacted inthe presence of a Lewis base catalyst.

DESCRIPTION OF THE RELATED ART

Formation of polyols using different methods is well known in the art.Specific types of polyols, e.g. those formed from epoxidized compounds,are also well known. These epoxidized compounds may have long chainhydrocarbon backbones, ester functionality, and internal and/or terminalepoxy groups.

The epoxidized compounds having terminal epoxy groups are known to reactwith a variety of curatives and hardeners such as primary, secondary,and tertiary amines, anhydrides, polyamides, borontrifluoride-monoethylamine complexes, dicyandiamides, polysulfides, andthiols. Protic curatives, such as primary and secondary amines havingthe formula RR′NH wherein R is alkyl group and R′ is either a hydrogenatom or an alkyl group, react with epoxidized compounds through additionreactions wherein one nitrogen-hydrogen group reacts with one epoxygroup of the epoxidized compound. This reaction is thought to proceedvia a primary or second amine attacking the terminal epoxy groupresulting in ring opening and the production of a zwitterion. Thezwitterion is capable of reacting with another epoxy group and openingthe ring. It is believed that this type of reaction continues until adense cross-linked structure including stable ether linkages is formed,as represented by the generic chemical reaction scheme and mechanismshown below:

These types of reactions proceed readily because the amine attacks aterminal epoxy group with minimal steric hindrance. However, if theepoxidized compounds have internal, i.e., non-terminal epoxy groups,ring opening reactions are much more difficult due to steric hindranceof surrounding groups such as aliphatic groups. These surrounding groupsrender internal epoxy groups much less reactive towards traditional ringopening polymerization reactants.

When epoxidized compounds having both internal and external epoxy groupsare reacted to form polyols, a number of different products are formeddue to both kinetic and thermodynamic considerations. This causes afinal product to have a wide polydispersity index, which is calculatedas a weight average molecular weight of the polyol divided by a numberaverage molecular weight of the polyol. The polydispersity indexrepresents a distribution of individual molecular masses of molecules ofthe polyol. As length and size of each molecule of the polyol approachuniformity, the polydispersity index approaches 1.0. The technologycurrently known in the art reacts epoxy groups according to themechanism described above and tends to cause a viscosity of the finalproduct to increase due to the formation of the dense cross-linkedstructure. This also increases the polydispersity index. In manyapplications, these increases in viscosity and polydispersity indicesare unacceptable. Accordingly, there remains an opportunity to developimproved polyols and an improved method of forming the polyols.

SUMMARY OF THE INVENTION AND ADVANTAGES

The present invention provides a polyol and a method of forming thepolyol. The polyol is the reaction product of an epoxidized oil and anorganic acid. The epoxidized oil and the organic acid are reacted in thepresence of a Lewis base catalyst. The Lewis base catalyst includes atleast one of a phosphorous atom or a nitrogen atom. The method offorming the polyol includes reacting the epoxidized oil with the organicacid in the presence of the Lewis base catalyst to form the polyol.

The particular Lewis base catalyst used in the present invention allowsthe organic acid to react with the epoxidized oil to form a polyolhaving hydroxyl groups and ester functionality in an efficient,accurate, and consistent manner. The Lewis base catalyst alsofacilitates ring opening of internal epoxy groups of the epoxidized oilwhile preserving other functional groups of the epoxidized oil, such astriglyceride ester skeletons. This ring opening allows the polyol togain additional hydroxyl groups and also allows for the customization ofpolyols with different functionalities. Further, the instant methodminimizes the formation of cross-linked structures and produces lessviscous polyols with narrowed ranges of polydispersity indices which aresuitable for use in a wide variety of applications. Still further, theinstant invention allows the polyol to be formed in an efficient andaccurate manner while minimizing production costs and maximizingconsistency.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

Other advantages of the present invention will be readily appreciated,as the same becomes better understood by reference to the followingdetailed description when considered in connection with the accompanyingdrawings wherein:

FIG. 1A is a diagram of a chemical structure of an exemplary soybeanoil;

FIG. 1B is a diagram of chemical structures and typical weight percentsof constituent fatty acids of soybean oil;

FIG. 1C is a diagram of a chemical structure of an exemplary epoxidizedsoybean oil;

FIG. 2 is an exemplary reaction scheme of the instant inventionincluding reaction of an epoxidized soybean oil and an organic acid suchas 2-ethylhexanoic acid, 2,2-dimethylolpropionic acid, and/or oleic acidin the presence of a Lewis base catalyst such as triphenylphosphineand/or triethylenediamine to form a polyol of the instant invention;

FIG. 3 includes one possible structure of the Comparative Polyol setforth in the Examples and an exemplary reaction scheme of a sidereaction which is reduced by the instant invention and which includesdimerization/cross-linking of epoxy groups;

FIG. 4A includes possible structures of the Polyols 1 and 2 of theinstant invention and set forth in the Examples; and

FIG. 4B includes one possible structure of Polyol 3 of the instantinvention that is set forth in the Examples.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention provides a polyol and a method of forming thepolyol. The polyol includes the reaction product of an epoxidized oiland an organic acid. In one embodiment, the polyol consists essentiallyof the reaction product of the epoxidized oil and the organic acid. Thisembodiment does not include additional reactants that react with theepoxidized oil and/or the organic acid because these additionalreactants would materially affect the basic and novel characteristic ofthe polyol. In another embodiment, the polyol consists of the reactionproduct of the epoxidized oil and the organic acid. The epoxidized oiland the organic acid are reacted in the presence of a Lewis basecatalyst. The Lewis base catalyst includes at least one of a phosphorousatom or a nitrogen atom. The organic acid and the Lewis base catalystare described in greater detail below.

The epoxidized oil may be formed from any natural or synthetic oil andhas at least one epoxy group. As is known in the art, epoxy groups arecyclic ethers with only three atoms in a ring. The ring forms anapproximately equilateral triangle with bond angles of about 60°, makingthe ring highly strained. This strain causes the epoxy groups to be veryreactive towards nucleophiles. The epoxidized oil may have both internaland terminal epoxy groups in any number. The epoxy groups may besymmetric and/or asymmetric epoxy groups such as those shown below:

wherein R is an organic or inorganic group.

In one embodiment, the epoxidized oil is formed from a natural oil, e.g.an oil derived from an animal or plant. One type of natural oil derivedfrom a plant is vegetable oil. Suitable non-limiting examples of oilsthat may be epoxidized include oils that have from 1 to 3 non-conjugatedcarbon-carbon double bonds such as chicken fat, canola oil, citrus seedoil, cocoa butter, corn oil, cottonseed oil, linseed oil, oat oil, oliveoil, palm oil, peanut oil, rapeseed oil, rice brain oil, safflower oil,sesame oil, soybean oil, sunflower oil, beef tallow, and combinationsthereof. In one embodiment, the oil that is epoxidized includes a highproportion of unsaturated constituent fatty acids. Typically, theepoxidized oil is derived from an animal or plant and reacted with aperacid, a perester, and/or a peroxide to form epoxy groups at sites ofcarbon-carbon double bonds. However, the epoxidized oil is not limitedto formation by such means. Preferably, the epoxidized oil has aviscosity of from 300 to 700, more preferably of from 400 to 600, andmost preferably of about 600, cps at 25° C. using a BrookfieldViscometer and a 21 spindle. Of course, the epoxidized oil is notlimited to such viscosities.

The epoxidized oil may be further defined as an epoxidized soybean oil.As is known in the art, soybean oils are common vegetable oils andtypically include unsaturated fatty acid chains such as linolenic acidchains, linoleic acid chains, and oleic acid chains, and saturated fattyacid chains such as stearic acid chains and palmitic acid chains, asshown in FIGS. 1A and 1B. In one embodiment, the epoxidized soybean oilincludes2-(8-(3-((3-hexyloxiran-2-yl)methyl)oxiran-2-yl)octanoyloxy)-3-(8-(3-((3-pentyloxiran-2-yl)methyl)oxiran-2-yl)octanoyloxy)propyl8-(3-octyloxiran-2-yl)octanoate,as shown in FIG. 1C. The epoxidized soybean oil may have numerous epoxygroups but is not limited to a certain number of epoxy groups permolecule, so long as the soybean oil includes at least one epoxy group.In various embodiments, the epoxidized soybean oil has one, two, three,four, or five internal epoxy groups. Of course, it is to be understoodthat the epoxidized oil may have more than five internal (or terminal)epoxy groups. It is believed that, in one embodiment, the soybean oil isapproximately 100 percent epoxidized and has the following approximatecharacteristics relative to constituent fatty acid chains:

Average Weight Percent of Number of Constituent Additional ConstituentNumber Average Fatty Acid Chains in Oxygen Atoms Fatty Acid MolecularWeight Epoxidized Soybean Added During Chains (g/mol) Oil (%)Epoxidation Palmitic Acid 256.4 10.41 0 Stearic Acid 284.5 4.03 0 OleicAcid 298.5 23.67 1 Linoleic Acid 312.5 54.41 2 Linolenic Acid 326.0 7.473Additionally, in this embodiment, the epoxidized soybean oil has anumber average molecular weight of about 944 g/mol, a weight averagemolecular weight of about 947 g/mol, a number average number of oxygenatoms per fatty acid chain of about 1.5, a weight average number ofoxygen atoms per fatty acid chain of about 1.55, a total number ofoxygen atoms per epoxidized soybean oil molecule of from about 4.49 to4.65, a number average oxygen content in the epoxidized soybean oil ofabout 7.62 percent, and a weight average oxygen content in theepoxidized soybean oil of about 7.85 percent. One suitable epoxidizedsoybean oil is commercially available from Arkema, Inc. of King ofPrussia, Pa.

The epoxidized oil may be combined with a non-epoxidized oil including,but not limited to, those non-limiting examples of oils described above.If the epoxidized oil is combined with the non-epoxidized oil, thecombination preferably includes at least 50%, and more preferablyincludes at least 75%, by weight of the epoxidized oil.

The epoxidized oil may be reacted with an additional polyol, such asglycerine, under transesterification conditions. Suitabletransesterification conditions include the use of an elevatedtemperature (such as from 70° C. to 180° C.) and the use of atransesterification catalyst such as a Lewis acid, tin and/or titaniumcompounds. The reaction of the epoxidized oil and the additional polyoltypically forms a mixture of glycerides (mainly mono- or di-glycerides)and esters of fatty acids. In one embodiment, the oil, prior toepoxidation, is reacted with the additional polyol to form a mixture ofoil-ester compounds, which are then epoxidized.

The additional polyol may include from 2 to 8 hydroxyl groups permolecule. More preferably, the additional polyol includes from 2 to 4,and most preferably includes from 3 to 4, hydroxyl groups per molecule.Mixtures of additional polyols may also be utilized. The hydroxylequivalent weight of the additional polyol is preferably less than 150and more preferably less than 75. Non-limiting examples of suitableadditional polyols include glycerine, trimethylolpropane, ethyleneglycol, propylene glycol, 1,4-butane diol, polymers of propylene glycoland/or ethylene glycol, pentaerythritol, sorbitol, sucrose,triethanolamine, triisopropanolamine, cyclohexane dimethanol, andcombinations thereof. Alkoxylates of any of the foregoing, such asethoxylates and/or propoxylates, can also be used. The additionalpolyols, or portions thereof, may also be esterified. In one embodiment,less than all of the hydroxyl groups of the additional polyols areesterified. Alternatively, all of the hydroxyl groups may be esterified.

As first described above, the epoxidized oil is reacted with an organicacid to form the polyol. The organic acid may be any known in the artthat includes at least one carbon atom. In one embodiment, the organicacid is further defined as a carboxylic acid. In another embodiment, theorganic acid includes a C₁-C₁₀ carbon chain and may be selected from thegroup of formic acid, acetic acid, propionic acid, butyric acid, valericacid, caproic acid, caprylic acid, capric acid, lactic acid, glycolicacid, 2-ethylcaproic acid, 2,2-dimethylolpropionic acid, 2-ethylhexanoicacid, hydroxybenzoic acid, and combinations thereof. Alternatively, theorganic acid may include more than 10 carbon atoms, may be a saturatedor unsaturated carboxylic acid, and may be selected from the group oflauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,linolenic acid, linoleic acid, acids including fatty acid chains havingat least one hydroxyl-functional ester group, and combinations thereof.It is also contemplated that the organic acid may be selected from thegroup of lactic acid, glycolic acid, 2,2-dimethylolpropionic acid, afatty acid chain having at least one hydroxyl-functional ester group,and combinations thereof.

In one embodiment, the organic acid is further defined as2-ethylhexanoic acid. For descriptive purposes only, a general chemicalstructure of 2-ethylhexanoic acid is shown below:

In another embodiment, the organic acid is further defined as2,2-dimethylolpropionic acid. For descriptive purposes only, a generalchemical structure of 2,2-dimethylolpropionic acid is shown below:

In yet another embodiment, the organic acid is further defined as oleicacid. A chemical structure of oleic acid is shown in FIG. 1B.

As is known in the art, carboxylic acids include a carboxyl group(COOH). In one embodiment, the carboxylic acid has two hydroxyl groups,i.e., an additional hydroxyl group. In another embodiment, thecarboxylic acid has three hydroxyl groups.

The organic acid may also include inorganic atoms such as silicon, i.e.,at least one silicon atom. Alternatively, the organic acid may includeat least one halogen atom. Suitable organic acids including at least onehalogen atom include, but are not limited to, haloalkane based acids,haloalkene based acids, haloaromatic based acids, acids such ashaloacetic acids, e.g. chloroacetic acid, organic acids including one ortwo halogen groups, and combinations thereof. Additionally, it iscontemplated that any of the aforementioned organic acids may bemodified to include at least one silicon or halogen atom and be used inthe instant invention. Alternatively, the organic acid may include acompound that reacts or decomposes to form the organic acid. Suitablenon-limiting examples of such compounds include lactides, glycolides,and combinations thereof.

Preferably the epoxidized oil and the organic acid are reacted in a moleratio of from 0.25 to 1.2, more preferably of from 0.5 to 1, and mostpreferably of from 0.75 to 1, moles of organic acid to one mole ofepoxidized oil. Without intending to be bound by any particular theory,it is believed that increasing a molar amount of the organic acidincreases a number of epoxy groups that are opened through a ringopening reaction. Conversely, it is believed that lowering a molaramount of the organic acid may increase cross-linking of epoxy groupsand/or viscosity of the polyol. Thus, the molar amounts of the organicacid to be used in forming the polyol may be chosen by one of skill inthe art based on desired physical properties of the polyol.Additionally, it is believed that, to increase a speed of reaction ofthe epoxidized oil and the organic acid, strong organic acids known inthe art may be used. However, weaker organic acids may also be used, aschosen by one of skill in the art.

The epoxidized oil and the organic acid are reacted in the presence ofthe Lewis base catalyst, as first described above. As is understood bythose of skill in the art, the Lewis base catalyst does notsubstantially react with either the epoxidized oil or the organic acid.Of course, the Lewis base catalyst may be protonated and/or deprotonatedin the instant invention. However, for purposes of this invention, thisprotonation/deprotonation is not a reaction because these productstypically are not stable.

The Lewis base catalyst includes at least one of a phosphorous atom or anitrogen atom. In other words, the Lewis base catalyst may include anitrogen atom to the exclusion of a phosphorous atom, a phosphorous atomto the exclusion of a nitrogen atom, or a nitrogen atom and aphosphorous atom. In one embodiment, the Lewis base catalyst is furtherdefined as an amine. In another embodiment, the Lewis base catalyst isfurther defined as a phosphine. Suitable non-limiting examples of Lewisbase catalysts include triethylenediamine (also known as1,4-diazabicyclo[2.2.2]octane and DABCO), DBU(1,8-diazabicyclo[5.4.0]undec-7-ene), DBN(1,5-diazabicyclo[4.3.0]non-5-ene),1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, hexamethylenetetramine,N-(2-cyanoethyl)morpholine), N-acetylmorpholine,N,N′-dimethylpiperazine,1,4-dimethyl-1H-pyrazole,2,2′dimorpholinediethylether, 2,4,6-(dimethylaminomethyl)phenol,N,N-ethyldiisopropylamine, N-ethylmorpholine, N-formylmorpholine,N-methylpiperazine, N-methyl-1H-pyrrole,1,3,5-(dimethylaminopropyl)-1,3,5-hexahydrotriazine,tris(2-ethylhexyl)amine, Ph₃P, PhPEt₂, PhPMe₂, Ph₂P(CH₂CH₂CN),PhP(CH₂CH₂CN)₂, (2,4,6-(OMe)₃C₆H₂)₃P, (4-F—C₆H₄)₃P, (4-CF₃—C₆H₄)₃P,P(CH₂CH₂CN)₃, Me₂PCH₂CH₂CN, bis(diphenylphosphino)methane,bis(diphenylphosphino)ethane), and combinations thereof. In oneembodiment, the Lewis base catalyst is selected from the group oftriphenylphosphine, triethylenediamine, and combinations thereof. Fordescriptive purposes only, chemical structures of triphenylphosphine andtriethylenediamine are shown below:

The epoxidized oil and the organic acid are preferably reacted in thepresence of the Lewis base catalyst in an amount of from 0.1 to 1, morepreferably in an amount of from 0.15 to 0.5, and most preferably in anamount of from 0.15 to 0.25, parts by weight per 100 parts by weight ofthe epoxidized oil and the organic acid.

Without intending to be bound by any particular theory, is it believedthat the epoxidized oil reacts with the organic acid in the presence ofthe Lewis base catalyst in a nucleophilic ring opening reaction toproduce hydroxyl groups (i.e., primary, secondary, and/or tertiaryhydroxyl moieties) and to add the organic acid to the epoxidized oil.More specifically, it is believed that under Lewis base catalysis,symmetrical epoxy groups may be attacked at either carbon atom whileunsymmetrical epoxy groups are preferentially attacked at a lesssubstituted, less sterically hindered carbon atom of the three memberring. Both symmetrical and unsymmetrical epoxy groups are believed to beattacked in a “S_(N)1 like” reaction. The epoxidized oil may react withthe organic acid in the presence of the Lewis base catalyst in areaction scheme as shown in FIG. 2. In one embodiment, the epoxidizedoil is further defined as epoxidized soybean oil, the organic acid isfurther defined as 2-ethylhexanoic acid, and the Lewis base catalyst isfurther defined as triethylenediamine.

Preferably, the epoxidized oil and the organic acid are reacted in thepresence of the Lewis base catalyst at a temperature of from about 50°C. to about 300° C., more preferably at a temperature of from about 100°C. to about 250° C., and most preferably at a temperature of from about140° C. to about 200° C. In one embodiment, the temperature is about150° C. In another embodiment, the temperature is about 200° C. Theepoxidized oil and the organic acid may be reacted under atmosphericpressure or at increased pressure and may be reacted under a noble gasatmosphere or under a nitrogen atmosphere. It is contemplated that useof shorter chain organic acids, e.g., those having less than or equal to10 carbon atoms, may allow for use of lower reaction temperatures.Alternatively, use of longer chain organic acids, i.e., those havingmore than 10 carbon atoms, may benefit from increased reactiontemperatures.

The epoxidized oil may be reacted with the organic acid in the presenceof the Lewis base catalyst and a solvent. The solvent may be any knownin the art and may include a non-polar solvent. Preferably, there is nosolvent present. However, one of skill in the art may choose a solventincluding, but not limited to, benzene, toluene, a halobenzene such aschlorobenzene, hexane, pentane, and combinations thereof.

The polyol formed in the instant invention typically has a hydroxylnumber of from 50 to 400, more typically of from 50 to 200, and mosttypically of from 60 to 90, mg KOH/g. The polyol also typically has afunctionality of up to about 13.2, more typically of from 2 to 6, andmost typically of from 2 to 4. Further, the polyol typically has anumber average molecular weight of up to 2,200, more typically of from1,000 to 2,000, and most typically of from 1,200 to 1,500, g/mol. Thepolyol also typically has a weight average molecular weight of up to3,000, more typically of from 1,000 to 2,000, and most typically of from1,500 to 1,900, g/mol. Further, the polyol typically has an acid numberof from 1 to 17 and more typically of from 0.1 to 17. Still further, thepolyol typically has an oxirane equivalent weight of from 0.1 to 4, moretypically of from 1.5 to 2.5, alternatively from 0.3 to 1.5 or from 0.7to 1.5, grams, determined by titration using methods well known in theart. As is known in the art, an oxirane equivalent weight of 0.1indicates that almost all of the epoxy groups in the epoxidized oil havereacted in a ring opening reaction. Conversely, an oxirane equivalentweight of 4 indicates that almost none of the epoxy groups in theepoxidized oil have reacted in a ring opening reaction.

The polyol also preferably has a viscosity of from 1,200 to 4,000 andmore preferably of from 1,600 to 3,700, cps at 25° C. using a BrookfieldViscometer and a 21 spindle. Additionally, the polyol typically has apolydispersity of from 1 to 3, more typically of from 1 to 2.5, and mosttypically of from 1.2 to 1.5. The polyol may also be formed with anincreased or decreased hydrophobicity, i.e., a ratio of carbon atoms tooxygen atoms in the polyol. It is believed that an increased ratiocontributes to flame retardancy and an increased number of oxygen atomsleads to increased hydrophilicity. Particularly suitable non-limitingexamples of polyols of the instant invention are set forth in FIGS. 4Aand 4B and are not intended to limit the instant invention.

The method of forming the polyol, first introduced above, includes thestep of reacting the epoxidized oil with the organic acid in thepresence of the Lewis base catalyst to form the polyol. The step ofreacting may also be accomplished by any way known in the art. In oneembodiment, the step of reacting is further defined as reacting theepoxidized oil and the organic acid in a “one-pot” synthesis. Forpurposes of the instant invention, the terminology “one-pot” means that,in this embodiment, the epoxidized oil is reacted with the organic acidin the presence of the Lewis base catalyst in a single reactor. In analternative embodiment, the step of reacting is further defined asreacting in a “two” or “multiple” pot synthesis in which two or morereactors are used. For example, a first portion of the epoxidized oilmay be reacted with a first portion of the organic acid in the presenceof a first portion of the Lewis base catalyst. Similarly, a second oradditional portion of the epoxidized oil may be reacted with a second oradditional portion of the organic acid in the presence of a second oradditional portion of the Lewis base catalyst.

As described above, the step of reacting may occur at a variety oftemperatures. That is, the step of reacting may be further defined asreacting at any of the temperatures described above. Further, the stepof reacting may occur at a variety of pressures. Typically, the step ofreacting occurs at or near atmospheric pressure. However, higher andlower pressures are also contemplated for use in this invention.

The step of reacting may proceed to completion, i.e., ˜100% of theepoxidized oil may react with ˜100% of the organic acid. Alternatively,the step of reacting may not proceed to completion and instead mayproceed to a percentage less than 99% or 100% completion. In oneembodiment, the step of reacting proceeds to less than or equal to about95% completion. If the reaction proceeds to less than completion, anamount of free organic acid may remain in the polyol. Typically, thisamount of free organic acid ranges from greater than zero to 10% byweight. In one embodiment, the polyol includes approximately 5% byweight of free organic acid. The step of reacting preferably yields thepolyol in a percentage yield of greater than 90%, more preferably ofgreater than 94%, and most preferably greater than or equal to 98%. Invarious embodiments, an amount of undesirable by-products due to sidereactions may be from greater than zero to 10% by weight of the polyol.Alternatively, the polyol may be free of undesirable by-products. Thecross-linking of non-reacted epoxy groups due to side reactions mayoccur via a dimerization reaction similar to the one set forth in FIG.3.

In one embodiment, the method includes the step of providing each of theepoxidized oil, the organic acid, and the Lewis base catalyst, which maybe accomplished via any way known in the art. The step of providing maybe further defined as adding each of the epoxidized oil, the organicacid, and the Lewis base catalyst into a reactor. The epoxidized oil,the organic acid, and the Lewis base catalyst may be added to thereactor in any order. In one embodiment, the organic acid and the Lewisbase catalyst are combined and added to the reactor followed by additionof the epoxidized oil. That is, in this embodiment, the organic acid andthe Lewis base catalyst are combined before reaction with the epoxidizedoil.

In one embodiment, the method consists essentially of the step ofreacting the epoxidized oil with the organic acid in the presence of theLewis base catalyst to form the polyol. In this embodiment, the methoddoes not include any additional reaction or reaction steps other thanthe step of reacting the epoxidized oil with the organic acid. Inanother embodiment, the method consists of the step of reacting. In afurther embodiment, the polyol is formed without the need for a “workup”step. As is known in the art, “working up” a reaction may includepurification and/or separation of a desired compound from a finalproduct in a reactor. In this embodiment of the invention, the polyolmay be used as made in the reactor with no purification or separationsteps required. Alternatively, the polyol may be “worked up,” ifdesired.

The method may be completed in a cycle time of from 2 to 14, morepreferably of from 2 to 12, and most preferably of from 2 to 6, hours.Without intending to be bound by any particular theory, it is believedthat by increasing amounts of the Lewis base catalyst and/ortemperature, the cycle time can be reduced.

The present invention also provides a resin composition comprising thepolyol of the instant invention. The resin composition may include oneor more additional polyols, different from the polyol of the instantinvention. These additional polyols may be any known in the art, may bederived from petroleum, and may include graft polyols. The resincomposition may also include additives, although additives are notrequired in the instant invention. The additives may be selected fromthe group of chain extenders, anti-foaming agents, processing additives,plasticizers, chain terminators, surface-active agents, adhesionpromoters, flame retardants, anti-oxidants, water scavengers, fumedsilicas, dyes, ultraviolet light stabilizers, fillers, thixotropicagents, silicones, transition metals, catalysts, blowing agents,surfactants, cross-linkers, inert diluents, and combinations thereof.The additives may be included in any amount as desired by those of skillin the art.

The additives may include amines. The additives may alternativelyinclude surfactants to stabilize the resin composition. The surfactantsmay be anionic, cationic, or non-ionic surfactants or may includemixtures of one or more surfactants. Further, the additives may includea blowing agents and/or blowing catalysts. The blowing catalysts may beused if the polyol is reacted with an isocyanate to form a foamedpolyurethane. More specifically, the blowing catalyst may increase aspeed of a reaction between the isocyanate and the water that formscarbon dioxide, as is known in the art. Further, the additives may alsoinclude gelling catalysts. Gelling catalysts typically promote areaction between the polyol and the isocyanate to form the polyurethane.Still further, the additive may include a foam surfactant. The foamsurfactant may be used to control cell size of polyurethane foams (e.g.,flexible polyurethane foams) produced from the reaction of the polyoland the isocyanate.

The present invention also provides a polyurethane including thereaction product of an isocyanate and the polyol of the instantinvention. It is also contemplated that the polyurethane may include thereaction product of the isocyanate, the polyol of the present invention,and one or more of the additional polyols of the resin composition,first introduced above. The polyurethane may be a flexible foam, a rigidfoam, an elastomer, or a non-foamed elastomer. The polyurethane may alsobe used in coatings, adhesives, and sealants.

The isocyanate may include any isocyanate known in the art including,but not limited to isocyanates, polyisocyanates, biurets of isocyanatesand polyisocyanates, isocyanurates of isocyanates and polyisocyanates,and combinations thereof. In one embodiment of the present invention,the isocyanate includes an n-functional isocyanate. In this embodiment,n is a number preferably from 2 to 5, more preferably from 2 to 4, andmost preferably from 3 to 4. It is to be understood that n may be aninteger or may have intermediate values from 2 to 5. The isocyanate mayinclude an isocyanate selected from the group of aromatic isocyanates,aliphatic isocyanates, and combinations thereof. In one embodiment, theisocyanate includes an aliphatic isocyanate. If the isocyanate includesan aliphatic isocyanate, the isocyanate may also include a modifiedmultivalent aliphatic isocyanate, i.e., a product which is obtainedthrough chemical reactions of aliphatic diisocyanates and/or aliphaticpolyisocyanates. Examples include, but are not limited to, ureas,biurets, allophanates, carbodiimides, uretonimines, isocyanurates,urethane groups, dimers, trimers, and combinations thereof. Theisocyanate may also include, but is not limited to, modifieddiisocyanates employed individually or in reaction products withpolyoxyalkyleneglycols, diethylene glycols, dipropylene glycols,polyoxyethylene glycols, polyoxypropylene glycols,polyoxypropylenepolyoxethylene glycols, polyesterols, polycaprolactones,and combinations thereof.

Alternatively, the isocyanate may include an aromatic isocyanate. If theisocyanate includes an aromatic isocyanate, the aromatic isocyanate maycorrespond to the formula R′(NCO)_(z) wherein R′ is aromatic and z is aninteger that corresponds to the valence of R′. Preferably, z is at leasttwo. If the isocyanate includes the aromatic isocyanate, the isocyanatemay include, but is not limited to, the tetramethylxylylene diisocyanate(TMXDI), 1,4-iisocyanatobenzene, 1,3-diisocyanato-o-xylene,1,3-diisocyanato-p-xylene, 1,3-diisocyanato-m-xylene,2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-1-nitro-benzene,2,5-diisocyanato-1-nitrobenzene, m-phenylene diisocyanate, p-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate,mixtures of 2,4- and 2,6-toluene diisocyanate, 1,5-naphthalenediisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4′-diphenylmethanediisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-biphenylenediisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate,3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, triisocyanates such as4,4′,4″-triphenylmethane triisocyanate polymethylene polyphenylenepolyisocyanate and 2,4,6-toluene triisocyanate, tetraisocyanates such as4,4′-dimethyl-2,2′-5,5′-diphenylmethane tetraisocyanate, toluenediisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethanediisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylenepolyphenylene polyisocyanate, corresponding isomeric mixtures thereof,and combinations thereof. Alternatively, the aromatic isocyanate mayinclude a triisocyanate product of m-TMXDI and 1,1,1-trimethylolpropane,a reaction product of toluene diisocyanate and 1,1,1-trimethyolpropane,and combinations thereof.

The isocyanate may have any % NCO content and any viscosity. Theisocyanate may also react with the polyol in any amount, as determinedby one skilled in the art. Preferably, the isocyanate and the polyol ofthe instant invention are reacted at an isocyanate index from 90 to 115,more preferably from 95 to 105, and alternatively from 105 to 110. Theisocyanate may also include any of the additives described above, inamounts determined by one of skill in the art.

EXAMPLES

Three polyols (Polyols 1-3) are formed according to the instantinvention. Specifically, to form each of the Polyols 1-3, an amount ofan Epoxidized Oil is reacted with an amount of an Organic Acid in thepresence of a Lewis Base Catalyst. Two Comparative Polyols (ComparativePolyols 1 and 2) are also formed but not according to the instantinvention. To form the Comparative Polyol 1, an amount of the EpoxidizedOil and the Organic Acid are reacted. No Lewis Base Catalyst is used toform the Comparative Polyol 1. To form the Comparative Polyol 2, anamount of the Epoxidized Oil and the Organic Acid are reacted in thepresence of water, which is used as a Lewis Base Catalyst that does notinclude any phosphorous or nitrogen atoms. The amounts of each of theEpoxidized Oil, the Organic Acid, and the Lewis Base Catalyst are setforth in Table 1 below wherein all amounts are in grams unless otherwiseindicated. After formation, each of the Polyols 1-3 and the ComparativePolyols 1 and 2 are characterized to determine hydroxyl number, acidnumber, oxirane equivalent weight, viscosity of the Polyol and residualorganic acid, color, polydispersity, and percent yield, which are alsoset forth in Table 1 below.

Formation of Polyol 1:

To form Polyol 1, 147.5 grams of oleic acid as the Organic Acid and 0.76grams of 1,4-diazabicyclo[2.2.2]-octane (DABCO) as the Lewis BaseCatalyst are added to a reaction flask to form a mixture. The reactionflask is equipped with temperature control, stirrer, reflux condenser,and an additional funnel. The mixture is then heated to approximately80° C. under a nitrogen (N₂) atmosphere. The temperature is held at 80°C. while 250 grams of epoxidized soybean oil (commercially availablefrom Arkema, Inc. of King of Prussia, Pa.) are added to the mixture. Themixture is then thoroughly mixed and heated to approximately 200° C. andheld at this temperature for approximately 6 hours. After 6 hours, thetemperature of the mixture is lowered to approximately 130° C., and avacuum is applied to reduce any residual water that may form. There isno additional workup of this reaction. After the vacuum is applied, apale yellow liquid including Polyol 1 is obtained.

Formation of Polyol 2:

To form Polyol 2, 147.5 grams of oleic acid as the Organic Acid and 250grams of epoxidized soybean oil are reacted in the presence of 1.35grams of triphenylphosphine, as the Lewis Base Catalyst, using the samemethod described immediately above. Polyol 2 is characterized in thesame ways described above relative to Polyol 1.

Formation of Polyol 3:

To form Polyol 3, 150.6 grams of 2-ethylhexanoic acid as the OrganicAcid and 500 grams of epoxidized soybean oil are reacted in the presenceof 1.24 grams of 1,4-diazabicyclo[2.2.2]-octane (DABCO), as the LewisBase Catalyst, using the same method described above for Polyol 1.Polyol 3 is characterized in the same ways described above relative toPolyol 1.

Formation of Comparative Polyol 1:

To form the Comparative Polyol 1, 150.6 grams 2-ethylhexanoic acid asthe Organic Acid is added to a reaction flask to and heated toapproximately 80° C. under a nitrogen (N₂) atmosphere. 500 gramsepoxidized soybean oil is then added to form a mixture. The mixture isthen thoroughly mixed and heated to approximately 150° C. and held for 6hours. After 6 hours, the temperature of the mixture is lowered and avacuum is applied to reduce any residual water that may form. After thevacuum is applied, a pale yellow liquid including the Comparative Polyol1 is obtained.

Formation of Comparative Polyol 2:

To form Comparative Polyol 2, 150.6 grams of 2-ethylhexanoic acid as theOrganic Acid and 1.24 grams of distilled water as a Lewis Base Catalystthat does not include any phosphorous or nitrogen atoms are added to areaction flask to form a mixture. The reaction flask is equipped withtemperature control, stirrer, reflux condenser, and an additionalfunnel. The mixture is then heated to approximately 80° C. under anitrogen (N₂) atmosphere. The temperature is held at 80° C. while 500grams of epoxidized soybean oil (commercially available from Arkema,Inc. of King of Prussia, Pa.) are added to the mixture. The mixture isthen thoroughly mixed and heated to approximately 200° C. and held atthis temperature for approximately 6 hours. After 6 hours, thetemperature of the mixture is lowered to approximately 130° C., and avacuum is applied to reduce any residual water that may form. There isno additional workup of this reaction. After the vacuum is applied, apale yellow liquid including Comparative Polyol 2 is obtained.

TABLE 1 Comparative Comparative Polyol 1 Polyol 2 Polyol 3 Polyol 1Polyol 2 Epoxidized Soybean 250 250 500 500 500 Oil Oleic Acid 147.5147.5 — — — 2-Ethylhexanoic — — 150.6 150.6 150.6 Acid DABCO 0.76 — 1.24— — Triphenylphosphine — 1.35 — — — Water — — — — 1.24 Uncorrected 64.680.6 105.5 90.2 118.9 Hydroxyl Number (mg KOH/g) Acid Number 0.62 2.547.7 15.9 12.8 (mg KOH/g) Oxirane Equivalent 0.60 0.44 0.93 0.80 0.85Weight Viscosity of the 1,760 2,070 3,380 4,210 4,190 Polyol + ResidualOrganic Acid (mPa · s at 25° C.) Viscosity ofthe >1,760 >2,070 >3,380 >4,210 >4,190 Polyol (mPa · s at 25° C.) ColorYellow Yellow Yellow Yellow Yellow Polydispersity 1.2 1.2 1.2 1.5 2.19 %Yield >98 >98 >98 >98 >98

Functionality, Hydroxyl Number, Acid Number, Oxirane Equivalent Weight,Viscosity, and Polydispersity are all determined by standard methodswell known in the art. Color is determined visually. Without intendingto be bound by any particular theory, it is hypothesized that Polyols1-3 have approximate chemical structures as set forth in FIGS. 4A and4B. It is also hypothesized that the Comparative Polyols 1 and 2 have anapproximate chemical structure as set forth in FIG. 3.

The only difference in the Polyols 1-3 and the Comparative Polyols 1 and2 is the use of the Lewis Base Catalyst of the instant invention in themethod of forming the Polyols. The Comparative Polyol 1 is formed withno catalyst whatsoever. The Comparative Polyol 2 is formed using wateras a Lewis Base Catalyst that does not include any phosphorous ornitrogen atoms. As the data set forth in Table 1 demonstrates, the AcidNumbers of the Comparative Polyols 1 and 2 are higher than the AcidNumbers of the Polyols 1-3. This indicates that the reactions to formthe Comparative Polyols 1 and 2 are not completed and that residualOrganic Acid is present in the Comparative Polyols 1 and 2. Morespecifically, the reaction to form the Polyols 1-3 proceeds furthertowards completion than the reactions that form the Comparative Polyols1 and 2.

The amount of residual Organic Acid present in the Polyols is related toviscosity. Viscosity is measured and reported in two ways in Table 1above. The first measurement of viscosity represents the viscosity ofthe Polyol and any residual Organic Acid and is reported in mPa·s at 25°C. Without intending to be bound by any particular theory, it isbelieved that the residual Organic Acid acts as an internal diluent andreduces this viscosity measurement. The Comparative Polyols 1 and 2 havehigher acid numbers, and therefore have more residual Organic Acid, thanPolyols 1-3 of the instant invention. Thus, the Comparative Polyols 1and 2 have more “internal diluent” yet still have a higher viscositythan Polyols 1-3. It is believed that, even without the “internaldiluent,” the Comparative Polyols 1 and 2 themselves are highlycross-linked, viscous, and undesirable.

The second measurement of viscosity represents the viscosity of thePolyols themselves, without any residual Organic Acid. As the data inTable 1 show, the viscosities of the Polyols themselves are higher thanwhen they include amounts of the Residual Organic Acid. The formation ofbyproducts affects the final polydispersity of the Polyols and theviscosity, as described above. Narrowed polydispersity indices indicatethat a more consistent final product (polyol) is formed. The data aboveshows that the Polydispersity Indices of the Comparative Polyols 1 and 2are higher than those of the Polyols 1-3. This means that the reactionsthat form the Comparative Polyols 1 and 2 are not as efficient as thereactions that form the Polyols 1-3 and produce more byproducts, whichare undesirable. Thus, the reactions that form the Polyols 1-3 are moreaccurate and more efficient.

Overall, the instant invention, which utilizes the Lewis Base Catalyst,produces polyols in an efficient, accurate, and consistent manner ascompared with the Comparative Polyols 1 and 2 and does so whileminimizing formation of cross-linked structures and producing lessviscous polyols with narrowed ranges of polydispersity indices. Thisallows polyols to be customized and manipulated based on market trendsand needs of individual users. This also allows polyols to be moreeasily used in commercial equipment due to the lower viscosities.

Additionally, a series of flexible foams (Foams 1-4) are formed usingPolyol 1 of the instant invention. A comparative foam (ComparativeFoam 1) is also formed using a petroleum based polyol that is not of theinstant invention. More specifically, these Foams are formed usingmethods well known in the art and include the formulations set forth inTable 2 below wherein all amounts are in grams unless otherwiseindicated.

TABLE 2 Comparative Foam 1 Foam 1 Foam 2 Foam 3 Foam 4 Petroleum Based100.0 95.0 90.0 80.0 60.0 Polyol Polyol 1 — 5.0 10.0 20.0 40.0 SiliconeSurfactant 1.0 1.0 1.0 1.0 1.1 Gel Catalyst 0.21 0.21 0.21 0.21 0.21Blowing Catalyst 0.03 0.03 0.03 0.03 0.03 Tin Catalyst 0.45 0.45 0.450.45 0.5 Water 3.15 3.15 3.15 3.15 3.15 Isocyanate, pbw 43.13 43.3343.54 43.95 44.77 TDI Index 110 110 110 110 110

The Petroleum Based Polyol is a trifunctional polyether polyol having anOH Number of 56 mg KOH/g.

The Polyol 1 is the same as Polyol 1 set forth in Table 1.

The Silicone Surfactant is commercially available from Union CarbideChemicals and Plastics Company, Inc. under the trade name of Niax®Silicone L-620.

The Gel Catalyst is commercially available under the trade name Dabco®33LV.

The Blowing Catalyst is commercially available under the trade nameDabco® BL11.

The Tin Catalyst is commercially available under the trade name Dabco®T-10.

The Isocyanate is toluene diisocyanate commercially available from BASFCorporation.

After formation, each of the Foams 1-4 and the Comparative Foam 1 isevaluated using ASTM D3574 to determine Density, Tear Strength, FallingBall Resilience, Indentation Force Deflection, Sag Factor, RecoveryPercentage, Air Flow, and Compression Force Deflection. The results ofeach of these determinations are set forth in Table 3 below.

TABLE 3 Comparative Foam 1 Foam 1 Foam 2 Foam 3 Foam 4 Density (pcf)1.81 1.80 1.83 1.75 1.84 Tear Strength (pi) 1.7 2.0 2.0 2.0 1.5 FallingBall 38 44 39 33 41 Resilience (%) Indentation Force Deflection (Lbs; 4inch) 25% Deflection 43.5 40.8 39.7 33.0 44.7 65% Deflection 76.4 73.071.8 64.6 79.7 Sag Factor 1.76 1.79 1.81 1.95 1.78 Recovery (%) 73 74 7369 73 AirFlow (cfm) 0.7 1.7 2.5 4.2 0.4 Compression Force 70 76 79 82 73Deflection % (of Orig. 50% Compression)

As the results in Table 3 demonstrate, the Foams 1-4 produced using thepolyol of the instant invention generally perform the same or betterthan the Comparative Foam 1 produced using the commercially availablepetroleum based polyol. Specifically, the Foams 1-4 consistently exhibitgreater tear strengths than the Comparative Foam 1. These results alsodemonstrate that the polyols of the instant invention can be used toreplace traditional petroleum based polyols resulting in minimizedproduction costs and a reduced use of petroleum.

The invention has been described in an illustrative manner, and it is tobe understood that the terminology which has been used is intended to bein the nature of words of description rather than of limitation.Obviously, many modifications and variations of the present inventionare possible in light of the above teachings, and the invention may bepracticed otherwise than as specifically described.

1. A method of forming a polyol comprising the step of reacting an epoxidized triglyceride soybean oil and an organic acid in the presence of a Lewis base catalyst comprising at least one of a phosphorous atom or a nitrogen atom to form the polyol wherein the polyol has a viscosity of from 1,200 to 4,000 cps at 25° C., and wherein the polyol has the following structure:

wherein R is an acid ester moiety derived from said organic acid.
 2. A method as set forth in claim 1 wherein the Lewis base catalyst is further defined as triethylenediamine.
 3. A method as set forth in claim 1 wherein the Lewis base catalyst is further defined as triphenylphosphine.
 4. A method as set forth in claim 1 wherein the organic acid is reacted in a molar ratio of from 0.5 to 1 moles of the organic acid per mole of the epoxidized triglyceride soybean oil.
 5. A method as set forth in claim 1 wherein the Lewis base catalyst and the organic acid are combined before reaction of the organic acid and the epoxidized triglyceride soybean oil.
 6. A method as set forth in claim 1 consisting essentially of the step of reacting the epoxidized triglyceride soybean oil and the organic acid in the presence of the Lewis base catalyst to form the polyol.
 7. A method as set forth in claim 1 consisting of the step of reacting the epoxidized triglyceride soybean oil and the organic acid in the presence of the Lewis base catalyst to form the polyol.
 8. A method of forming a polyol, said method consisting essentially of the steps of: A. providing an epoxidized triglyceride soybean oil; B. providing an organic acid selected from the group of 2-ethylhexanoic acid, oleic acid, 2,2-dimethylolpropionic acid, and combinations thereof in a mole ratio of from 0.5 to 1 mole of the organic acid per mole of the epoxidized triglyceride soybean oil; C. providing a Lewis base catalyst selected from the group of triethylenediamine, triphenylphosphine, and combinations thereof; and D. reacting the epoxidized triglyceride soybean oil and the organic acid in the presence of the Lewis base catalyst at a temperature of from 140° C. to 200° C. to form the polyol wherein the polyol has a viscosity of from 1,200 to 4,000 cps at 25° C., wherein the polyol has the following structure:

and wherein each R is independently selected from the group of:


9. A method as set forth in claim 1 wherein each R is independently selected from the group of:


10. A method as set forth in claim 9 wherein the polyol has a polydispersity of from 1.2 to 1.5.
 11. A method as set forth in claim 1 wherein the polyol has a polydispersity of from 1.2 to 1.5.
 12. A method as set forth in claim 1 wherein the organic acid is selected from the group of 2-ethylhexanoic acid, oleic acid, 2,2-dimethylolpropionic acid, and combinations thereof. 